Gasolene composition containing organometallic orthophosphates



United States Patent 3,231,347 GASOLENE COMPOSITION CONTAININGORGANOMETALLIC ORTHOPHOSPHATES Anthony J. Revukas, Crantord, N.J.,assignor to Cities Service Oil Company, Bartlesville, Okla., acorporation of Delaware No Drawing. Original application July 31, 1961,Ser. No. 127,840. Divided and this application Apr. 26, 1963, Ser. No.279,695

Claims. ((31.44-69) This application is a division of application SerialNo. 127,840, filed July 31, 1961.

This invention relates to novel metallic orthophosphate compounds and togasolene compositions including such compounds.

The use of lead compounds to increase the octane rating of gasolene isextremely common. Unfortunately, the addition of lead, whilesubstantially increasing the octane ratings of gasolenes to which it isadded, at the same time has several drawbacks. Of these drawbacks themost serious is probably the tendency of the lead to increaseundesirable surface ignition in the combustion chambers of the internalcombustion engines in which the leaded gasolene is used. It has been thepractice previously to utilize various phosphorous compounds in anattempt to reduce or prevent such surface ignition, but the use of suchcompounds has. generally led to additional difficulties such as leaddeposits on cylinder heads and valves.

It is an object of the present invention to provide novel metallicorthophosphate compounds adapted for use in improved gasolenecompositions.

It is another object of the invention to provide an improved gasolenecomposition especially adapted to resist surface ignition.

This application is a continuation-in-part of my copending applicationSerial No. 27,294, filed May 6, 1960 for Titanium Orthophosphates.

The novel compounds of the present invention are orthophosphates oftitanium or zirconium. Preferred orthophosphates of these metals may berepresented by the general formula RO O I: II I M P 0 wherein Mrepresents zirconium or titanium, X is a number equal to the valence ofthe metal M and R and R each represent a hydrocarbon radical having from2 to carbon atoms. In such compounds titanium and zirconium each has avalence of either 3 or 4 depending upon the starting material used.Preparation of these compounds is discussed in greater detail below. Rand R may represent identical or diiferent hydrocarbon radicals. Whileany hydrocarbon radicals having between 2 and about 30 carbon atoms andsoluble to the required extent in gasoene may be used, at least one of Rand R preferably represents a branched chain hydrocarbon radical. Suchradicals are generally more soluble in gasolene than other hydrocarbonradicals, thereby facilitating the use of the novel compounds of thepresent invention as gasolene additives. Since chains of more than about30 carbon atoms are generally ditficult or impossible to dissolve ingasolene compositions, it is preferred that the hydrocarbon radicals ofthe orthophosphates of the present invention each have between 2 andabout 30 carbon atoms.

Compounds of the present invention having branched chain alkylhydrocarbon radicals include for instance the following:

Titanium tetra (bis(2-m'ethylpropyl) orthophosphate) Zirconium tetra(bis(3-butyloctosyl) orthophosphate) "ice Titanium tetra(bis(5-pentylhexadecyl) orthophosphate) Titanium tetra(bis(Z-ethyl-S-butyltridecylJ orthophosphate) Zirconium tetra(bis(2-propyldecyl) orthophosphate) Titanium tetra(bis(2,4-diethyloctyl) orthophosphate Titanium tetra(bis(2-rnethyloctyl) orthophosphate) Zirconium tetra (bis(methylethyl)orthophosphate) Titanium IV di(2-ethylhexyl), tributyl orthophosphateTitanium tetra (bis(methylethyl) orthophosphate) Titanium tetra(Z-methylpropyl, methyleth'yl orthophosphate) Titanium tetra(Z-methyloctyl, 2-propyldecyl orthophosphate) Titanium IVdi(2-ethylhexyl), di(methylethyl), di-(Z- methylpropyl),di(3-butyloctosy1) orthophosphate Titanium tri (bis(2-ethylhexyl)orthophosphate) Zirconium tetra (bis(2-ethyl-hexyl) orthophosphate)Zirconium tri (Z-ethylh'exyl, Z-methylpropyl orthophosphate) Compoundsof the present invention having alkylaryl hydrocarbon radicals includefor instance, the following: Titanium tetra (bis(octylpheny1)orthophosphate) Zirconium tetra (bis(methylphenyl) orthophosphate)Titanium tetra (bis(tricosylphenyl) orthophosphate) Zirconium tetra(bis(pentylphenyl) orthophosphate) Titanium tetra (octylphenyl,phentylphenyl orthophosphate) Titanium tri (bis(methylphenyl)orthophosphate) Zirconium tri (bis(hexylphenyl) orthophosphate)Compounds of the present invention having both alkyl and alkylarylhydrocarbon radicals include, for instance,

Zirconium tetra (2-ethylhexyl, methylphenyl) orthophosphate) Titanium IVdi(-2-ethylhexyl), di(octylphenyl), 2-propyldecyl, methylethyl,di(2-methyloctyl) orthophosphate Compounds of the present inventionhaving straight chain hydrocarbon radicals include for instance thefollowing:

Zirconium tetra (bis(octyl) orthophosphate) Titanium tetra (bis(ethyl)orthophosphate] Titanium tetra (methyldecyl orthophosphate) Zirconium IVdibutyl, dihexyl, ethylhexyl, dipentyl orthophosphate Titanium tetra(octylphenyl, heXyl orthophosphate) Zirconium tetra (2-ethylhexyl, butylorthophosphate) Zirconium tetra (pentacosyl, hexadecyl orthophosphate)Titanium tri (bis(ethyl) orthophosphate) Zirconium tri (Z-ethylhexyl,butyl orthophosphate) The novel compounds described above are especiallyuseful as gasolene additives in forming novel gasolene compositionsadapted to resist surface ignition. In addition to resisting surfaceignition, these additives generally inhibit rust and carburetor icing.In accordance with a preferred embodiment of the present invention agasolene composition is provided which comprises a major proportion of aleaded hydrocarbon base fuel boiling in the gasolene range andcontaining between about 0,001 and about 5.0 theories of a titanium orzirconium orthophosphate. Such metallic orthophosphate preferably is ofthe type described above having the general formula By the term leadedgasolene, leaded hydrocarbon base fuel boiling in the gasolene range andsimilar terms is meant a petroleum fraction boiling in the gasoleneboiling range (e.g., between about and about 450 F.) to which has beenadded a small amount, such as between about 0.1 and about 6.0 cc. pergallon, of a metallo-organic antiknock compound such as tetraethyl lead(TEL), tetramethyl lead (TML), tetraisopropyl lead, etc. Lead isfrequently present in gasolene compositions of the present invention inthe form of TEL, TML or mixtures of the same which may be present insuitable amounts such as between about 0.1 and about 6.0 cc. per gallonof gasolene composition, more usually between about 0.5 and about 4.0cc. per gallon.

The novel metallic orthophosphates described above for use in leadedgasolene compositions in accordance with the present invention arepresent in suitable amounts such as between about 0.001 and about 5.0theories, preferably between about 0102 and about 2.0 theories. The

term theory 'is'int'ended in this"context'to designate the amount ofadditive required for the metal in the additive to reactstoichiometrically with the lead in the compound such as TEL to producethe appropriate compound such as lead metatitanate.

In addition to the above described titanium and lead compounds, gasolenecompositions contemplated by the present invention may include one ormore other ingredients such as lead scavengers, gum inhibitors,lubricants, rust inhibitors, metal deactivators or other special purposeadditives.

Lubricants suitable for use in the above described gasolene compositionsmay include, for instance, light hydrocarbon lubrcating oils havingviscosities at 100 F. of between about 50 and about 200 saybolt.universal seconds (SUS) and viscosity indexes (VI) of between about 30and about 120' with oil having a viscosity of about 100 SUS beingpreferred. Such oils may be present in suitable amounts such as betweenabout 0.1 and about 1.0 volume percent of the gasolene composition.

When using lead compounds such as TEL, it is frequently found desirableto include with the lead a suitable lead scavenger for reducing thedeposit of lead compounds within the combustion chamber. Such leadscavengers include for example halohydrocarbon compositions such asethylene dibromide and ethylene dichloride.

Gum inhibitors suitable for use in the above described gasolenecompositions include conventional gum inhibitors such as2,6-ditertiary-butylpa-ra cresol. Such gum inhibitors may be present insuitable amounts such as between about 0.001 and about 0.006 volumepercent of the gasolene composition. Likewise, a suitable metaldeactivator is for example N,Ndisalicylidene-1,2-diaminopropane.

An especially valuable titanium compound of the type described above foruse in gasolene compositions of the type described above is titaniumtetra (bis(2-ethylhexyl) orthophosphate) having the formula i andhereinafter referred to as TIP.

Gasolene compositions of the present invention may be illustrated by thefollowing examples. In most of these examples the gasolene compositionsof the present invention are described as containing TIP. While TIl andthe corresponding zirconium compound are preferred additives for use insuch gasolene compositions, it should be understood that any of theother novel additive compounds contemplated by the invention, such asthose described above, may be-used in such gasolene compositions inplace of or in addition to the TIP.

Example 1 A gasolene composition having excellent surface ignitioncharacteristics may be prepared by adding the following ingredients to asuitable base gasolene:

TEL 2.2 cc. per gallon. TIP 0.05 theory.

The base gasolene used in blending this and other gasolene compositionsof the invention may be a gasolene having the following characteristics:

Another suitable gasolene composition is prepared by adding thefollowing ingredients to a suitable base gasolene:

TEL Q 0.5 cc. per gallon. TIP 0.25 theory.

Example 4 Another suitable gasolene composition is prepared by addingthe following ingredients to a suitable base gasolene:

TEL 4.0 cc. per gallon. TIP 0.5 theory. I

Lubricating Oil 1.0 volume percent (100 SUS, VI).

Example 5 Another suitable gasolene composition is prepared by addingthe following ingredients to a suitable base gasolene:

TEL 6.0 cc. per gallon. TIP 5.0 theory.

Example 6 Another suitable gasolene composition is prepared by addingthe following ingredients to a suitable base gasolene:

TEL a. 0.1 cc. per gallon. TIP 0.005 theory.

Example 7 Another suitable gasolene composition is prepared by addingthe following ingredients to a suitable base gasolene:

TEL 1.5 cc. per gallon. TIP 0.01 theory. Lubricating Oil 0.1 volumepercent SUS, 95 VI).

Example 8* Another suitable gasolene composition is prepared by addingthe following ingredients to a suitable base gasolene:

TEL 3.0 cc. per gallon. Zirconium tetra bis(octylpheny1) orthophosphate2.0 theory.

Example 9 Another suitable gasolene composition is prepared by addingthe following ingredients to a suitable base gasolene:

TEL 2.0 cc. per gallon. Titanium tetra bis(octylphenyl) orthophosphate0.5 theory.

Example 10 Another suitable gasolene composition is prepared by addingthe following ingredients to a suitable base gasolene:

TEL 2.2 cc. per gallon. TIP 0.1 theory.

Lubricating Oil 025 volume percent (100 SUS, 95 VI).

Novel additive compounds of the type described above may be prepared inany suitable manner. According to one method of preparation, a suitableorganic hydrogen phosphate or a mixture of such phosphates is placed ina reaction flask together with about half its volume of a suitablesolvent such as dry toluene. The reaction flask is preferably equippedwith a mechanical stirrer, thermometer, gas inlet tube, reflux condenserand a pressure equalizing funnel with its long stem dipping into thesolution. The temperature in the reaction flask is raised to betweenabout 110 and about 130 C. while stirring vigorously and titanium orzirconium tetrachloride with an equal volume of the solvent is added inspurts by means of the pressure equalizing delivery funnel. Thetetrachloride .is preferably introduced in amounts of about 1.1 moles oftetrachloride for each 4 moles of the organic hydrogen phosphate.Hydrogen chloride is evolved copiously by the reaction. Stirring andheating under reflux to 130 C. is continued until evolution of hydrogenchloride stops. Removal of byproduct hydrogen chloride is promoted byflushing the reaction flask with dry nitrogen by means of the gas inlettube. The solvent is removed by distillation at reduced pressure such as10 to millimeters, the final temperature being about 130 C. The yield ofproduct is usually between about and about of theory based and hydrogenphosphate.

In compounds prepared as described immediately above, the titanium orzirconium has a valence of 4. Similar compounds in which these metalshave a valence of 3 may be prepared in a similar manner, e.g., by usingtitanium or zirconium trichloride rather than tetrachloride as astarting material.

Example 11 In the production of TIP by means of the above procedure 2000grams of commercial di(2-ethylhexyl) hydrogen phosphate (6 moles) and330 grams (1.7 moles) of titanium tetrachloride were brought intoreaction. The resulting solvent-free crude product was washed with Waterto remove acidic materials, taken up in half its volume of normalpentane, and dried over anhydrous sodium sulfate. After filmring, thepentane Was removed by distillation with the final temperature being C.at 20 millimeters pressure. The yield of dark, amber colored liquid TIPwas 1900 grams or 95% of theory based on acid phosphate. Percentages oftitanium and This TIP had a viscosity at 100 F. of 1337 SUS and at 210F. of 180 SUS. The density of this TIP at 20 C. was 1.055.

In forming the TIP as described above the reaction is formulated asfollows:

In order to demonstrate the usefulness of novel compounds of the typedescribed above which include alkyl aryl radicals as gasolene additives,titanium tetra (bis (octylphenyl) orthophosphate) was prepared inaccordance with the general method of preparation described above. Thiscompound was solid but Was moderately soluble in gasolene and is,therefore, suitable as a gasolene additive.

Example 13 Another titanium orthophosphate containing branched chainhydrocarbon radicals was prepared by reacting 0.2 mole each of monobutylhydrogen phosphate, dibutyl hydrogen phosphate and di(2-ethylhexyl)hydrogen phosphate with 0.22 mole titanium tetrachloride in the mannerdescribed above. A 92% yield based on titanium tetrachloride wasobtained of titanium IV di(2--ethylhexyl)tri butyl orthophosphate havingthe formula:

This compound Was a resinous amber colored solid which was soluble ingasolene. An analysis for titanium yielded the following results:

Percent Theory 6.56 Actually found 6.55

Example 14 Zirconium orthophosphate was prepared according to thegeneral procedure described above by reacting 0.11 mole of zirconiumtetrachloride with 0.40 mole of di(2- ethylhexyl) hydrogen phosphate inthe presence of 300 milliliters of toluene. The product was zirconiumtetra (bis(2-ethylhexyl) orthophosphate) having the formula:

CzHu 2 4 In order to evaluate the characteristics of gasolenecompositions of the present invention, three separate gasolenecompositions (A, B, and C) were prepared These gasolene compositionscontained metallic orthophosphate additives of the present invention asindicated in Table I and II below.

Gasolene compositions A and B used the base gasolene described above .inConnection with Example 1 with 2.2 cc. per gallon of TEL added. Gasolenecomposition C also used a base gasolene having the same properties asthe base gasolene of Example 1. The base gasolene of Example C alsocontained 2.2 cc. per gallon of TEL but had been stored for a shorterperiod of time prior to the tests described below than had the basegasolenes of gasolene compositions A and B. The base gasolenes ofgasolene compositions B and C also contained 0.25 volume percent of 100SUS (95VI) light lubricating oil. The base gasolenes of gasolenecompositions A, B and C thus 8 TABLE I Single cylinder engine deposittest differed from the compositions A, B and C respectively Avemfle WildPin 8 only in the presence or absence of the metallic orthophosler HourBase Gasoline Orthophosphate Theories Gasoline phate additives of thepresent invention. The gasolene Composition Additive of compositions A,B and C, as well as their respective base Additive gasolenes weresubjected to both single cylinder and multil q i h additive additivecylinder engine deposit tests as described below.

The single cylinder engine deposit tests were run in A TIP 0 05 2 CFRengines having L head assemblies and compression )3 IP E.E- 6 8. as L 4I llCOnlllIl'l 6 re 18 9S5 ratios of to 1. Each test consisted ofalternating periods (zethylhexyl) mm than 1 of operation under idlingconditions for 50 seconds fol- P p lowed by operation under'full loadconditions for 150 15 TABLE II Mwlticylinder engine deposit test OctaneRequirement LIB Requirements Increase (0 RI) Base Base Gasoline GasolineTheories of asoline Composition Orthophospliate Additive AdditiveWithout With Without With additive additive additive additive A TIP 0.05 i4. 5 5. 5 s5 55 B TIP 0. 10 14. 5 4. 5 C Zirconium tetra (bis(2-ethyl- 0.20 24. 8 5. 2 100 plus 60 hexyl) orthosphosphate).

seconds. These cycles were continued for a total test time of at leasthours for each test. During these tests the engine air intaketemperature was maintained at 115 F. while the oil temperature wasmaintained at 160 F. and the coolant temperature at 150 F. During theidling portions of the test-s the engines were operated with an air tofuel ratio of 12 to 1 at 600 r.p.m. while during the full load portionsof the tests the engines were operated with air to fuel ratios of 13 to1 and at 900 r.p.m. During the test, the number of wild pings(indicating preignition) was counted by an Erwin Instrument Co. WildPing Counter. At the end of the test the average of the wild pings perhour was determined by plotting the total wild pings versus time andtaking the slope of the curve. This measurement served as a reliableindication of the surface ignition characteristics of the fuel beingtested.

The multi-cylinder engine deposit tests were run in 1958 OldsmobileRocket Engines having compression ratios of 10 to 1. The total time ofeach of these tests was 120 hours of operation in cycles of 50 secondsoperation under idling conditions followed by 150 seconds operationunder load conditions to develop twelve brake horsepower. During theidle portions of the cycle the engines were operated with an air to fuelratio of 12 to 1 at a speed of 600 r.p.m. and with a coolant temperatureof 160 F. During the load portions of the test the engines were operatedwith an air to fuel ratio of 14 to 1 at 2000 r.p.m. and with a coolanttemperature of 160 F. Oil temperature was not controlled during thesetests. At intervals of 16 to 24 hours the Octane Requirement Increase(ORI) was obtained by full throttle operation at 1000 r.p.m. usingprimary reference fuels and Varying spark advance for trace knock. Atthe end of the test the LIB requirement (Leaded Isooctane-Benzenereference fuel with 3 cc. per gallon TEL to yield trace rumble) wasobtained. The LIB requirement was obtained at 1500 r.p.m. and was theLIB fuel needed to prevent rumble at wide open throttle.

The results of the single cylinder engine deposit test on the gasolenecompositions A, B and C and their respective base gasolenes describedabove are given in Table I below while the results of the multicylinderengine deposit tests are given in Table II.

Table I shows clearly that the addition of the titanium or zirconiumorthophosphate to the base gasolenes resulted in gasolene compositionshaving remarkably good surface ignition characteristics as evidenced bya decrease in wild pings as compared with the base gasolenes which didnot contain these additives. Likewise, Table II indicates clearly thatthe addition of the zirconium or titanium orthophosphate substantiallyreduced the octane number increases due to engine deposits as well asthe LIB requirements. For instance, with TIP in the gasolene theOldsmobile engines tolerated a three times greater amount of the surfaceignition inducing aromatic benzene then did the base gasolene, therebyfurther attesting to the high surface ignition resistance quality of thegasolene composition containing the metallic ort-hophosphates of thepresent invention.

In order to evaluate the ability of TIP to inhibit carburetor icing,carburetor icing tests were conducted in a standard six cylinderChevrolet engine having a displacement of 216.5 cubic inches and ratedat 86 horsepower at 3400 r.p.m. The following test conditions wereemployed.

Intake air 38 to 40 F. Relative humidity Engine load 10 horsepower.Engine speed 1500 r.p.m.

Idle speed 450 to 500 r.p.m.

Temperature of fuel entering carburetor- 48 to 50 F.

Air to fuel ratio n 12.3 to 12.5.

Carburetor icing tendencies of gasolenes are measured by this test whenthe engine is operated under the constant severe icy conditions outlinedabove. The engine run is started with the throttle plate at 34 F. Theice forming characteristics of the test gasolene normally control theengine operating cycle. During the test the engine is run at 1500 r.p.m.for 1 to 2% minutes. At the end of the 1500 r.p.m. operating cycle thethrottle is returned to the idle speed of 450 to 500 r.p.m. The engineis idled for 30 seconds and is stalling does not occur the idle speedr.p.m. is observed. A reduction in idle speed of more than 100 r.p.m. isconsidered a partial stall.

The base gasolene used in the carburetor icing tests had the followingvolatility characteristics:

Gravity .3 API 60.0 Reid vapor pressure lbs 10.9 ASTM distillation F.):

IBP F 81 5% evaporated 102 112 70 250 90 315 95 335 EP 359 Recoverypercent 97.4 Residue do 1.1 Loss do 1.5

A total of 12 test runs were made. In four of these runs the basegasolene contained no additive except 2.2 cc. per gallon TEL. In anotherseries of four runs the base gasolene used contained 0.024 theory TIPwhile in the remaining four runs the base gasolene contained 0.096theory TIP. The results of these carburetor icing tests are shown inTable III below. 0

TABLE III Stalling characteristics of gasolene with and without TIPAmount of TIP in Base Gasolene (theories) Operating Time at Idle (min) Sindicates stalling occurred. N indicates no stalling occurred.

The results show clearly that when TIP was not used the engine stalledwithin A2 to 1 minute after the throttle was returned to the idleposition. Stalling is attributable to ice formation around the peripheryof the throttle plate when it was nearly closed at idle. During theseruns the ice was observed to build up, particularly in the throttleplate swivel area, thereby restricting the air flow. Such icing isespecially prevalent in the wintertime because the more volatile wintergrade gasolenes aggravate icing tendencies due to their greater tendencyto evaporate with resulting cooling. Also, weather conditions frequentlyintroduce enough moisture to create icing problems when relativehumidity of the atmosphere is above about 85% and the temperaturebetween about and about 47 F. In contrast to the poor stallingcharacteristics displayed by the base gasolene under the test conditionsdescribed above, the gasolene containing TIP prevented ice build up inthe throttle plate zone as observed visually during the test and also asdemonstrated by the absence of stalling during 3% minutes of engineoperation with the throttle in idle position during the above describedtest. It is, therefore, apparent that the addition of TIP to the basegasolene served to eliminate the stalling tendencies of the basegasolene. TIP is thus shown to be a superior gasolene additive in thatit not only reduced preignition problems as described above, but alsoreduces or eliminates carburetor icing and prevents rusting asdetermined by ASTM Method D665- 54 Test for Rust-PreventionCharacteristics of Oil, when performed at ambient temperature.

While the invention has been described above with re spect to certainpreferred embodiments thereof, it will be understood by those skilled inthe art that various changes wherein M is a metal selected from thegroup consisting of titanium and zirconium and each of R and R is ahydrocarbon radical having between 2 and about 30 carbon atoms in thelongest chain.

2. A gasolene composition comprising a major proportion of a leadedhydrocarbon base fuel boiling in the gasolene range and containingbetween about 0.001 and about 5 .0 theories of an additive having theformula:

wherein M is a metal selected from the group consisting of titanium andzirconium, X is a number equal to the valence of the metal M and each ofR and R is a hydrocarbon radical having between 2 and about 30 carbonatoms in the longest chain.

3. The gasolene composition of claim 2 in which the least one of R and Ris a branched chain hydrocarbon radical.

4. The gasolene composition of claim 2 in which the metal is titanium.

, 5. The gasolene composition of claim 2 in which R and R are branchedchain alkyl hydrocarbon radicals.

6. The gasolene composition of claim 2 in which R and R are identicalbranched chain alkyl hydrocarbon radicals.

7. The gasolene composition of claim 2 in which R and R are identicalbranched chain alkyl aryl hydrocarbon radicals.

8. The gasolene composition of claim 2 in which the additive is titaniumtetra(bis(2-ethylhexyl) orthophosphate).

9. A gasolene composition comprising a major proportion of a hydrocarbonbase fuel boiling in the gasolene range and containing between about 0.5and about 4.0 cc. per gallon tetraethyl lead and between about 0.2 andabout 2.0 theories of titanium tetra(bis(2-ethylhexyl) orthophosphate)10. A gasolene composition comprising a major proportion of a leadedhydrocarbon base fuel boiling in the gasolene range and containingbetween about 0.001 and about 5.0 theories of titanium tetra bis(octylphenyl) orthophosphate.

11. A gasolene composition comprising a major proportion of a leadedhydrocarbon base fuel boiling in the gasolene range and containingbetween about 0.02 and about 2.0 theories of an additive having theformula:

wherein M is a metal selected from the group consisting of titanium andzirconium, X is a number equal to the valence of the metal M and each ofR and R is a phate) References Cited by the Examiner UNITED STATESPATENTS 2,228,659 1/1941 Farrington 25239 X 2,346,155 4/1944 Denison252-32 X 2,863,742 12/1958 Cantrell 44--72 X 3,007,782 11/1961 Brown4456 3,014,792 12/1961 Capowski 4456 3,035,906 5/1962 Hinkamp 44563,055,925 9/1962 Hartle 260-437 3,116,248 12/1963 Frew 252389 X3,116,249 12/1963 Ratner 252389 X DANIEL E. WYMAN,Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,231,347 January 25, 1966 Anthony J. Revukas It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

line 27, for "phentylphenyl" read pentylphenyl line 33, after"instance," insert the following:

line 28, for "lubrcating" read lubricating column 3,

line 44, for "and" read on column 6, lines column 5 8 to 10, the formulashould appear as shown below instead of as in the patent:

Column 2,

4HCl+Ti OP (0) OCH .CH\

i wer portion of the formula lines 32 to 39, the lo n the patent:

same column 6 should appear as shown below instead of as i column 8,line 72, for "is", second occurrence, read if column 9, line 8, after"evaporated" insert line 71, for "Rust-Prevention" read Rust-Preventingcolumn 10, line 35, for "the" read at Signed and sealed this 20th day ofDecember 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A GASOLENE COMPOSITION COMPRISING A MAJOR PROPORTION OF A LEADEDHYDROCARBON BASE FUEL BOILING IN THE GASOLENE RANGE AND CONTAININGBETWEEN ABOUT 0.001 AND ABOUT 5.0 THEORIES OF AN ADDITIVE HAVING THEFORMULA: